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121.
Dongyi Liu Ahmed M. El‐Zohry Maria Taddei Clemens Matt Laura Bussotti Zhijia Wang Jianzhang Zhao Omar F. Mohammed Mariangela Di Donato Stefan Weber 《Angewandte Chemie (International ed. in English)》2020,59(28):11591-11599
We prepared conceptually novel, fully rigid, spiro compact electron donor (Rhodamine B, lactam form, RB)/acceptor (naphthalimide; NI) orthogonal dyad to attain the long‐lived triplet charge‐transfer (3CT) state, based on the electron spin control using spin‐orbit charge transfer intersystem crossing (SOCT‐ISC). Transient absorption (TA) spectra indicate the first charge separation (CS) takes place within 2.5 ps, subsequent SOCT‐ISC takes 8 ns to produce the 3NI* state. Then the slow secondary CS (125 ns) gives the long‐lived 3CT state (0.94 μs in deaerated n‐hexane) with high energy level (ca. 2.12 eV). The cascade photophysical processes of the dyad upon photoexcitation are summarized as 1NI*→1CT→3NI*→3CT. With time‐resolved electron paramagnetic resonance (TREPR) spectra, an EEEAAA electron‐spin polarization pattern was observed for the naphthalimide‐localized triplet state. Our spiro compact dyad structure and the electron spin‐control approach is different to previous methods for which invoking transition‐metal coordination or chromophores with intrinsic ISC ability is mandatory. 相似文献
122.
Thermally Activated Delayed Fluorescence in a Y3N@C80 Endohedral Fullerene: Time‐Resolved Luminescence and EPR Studies
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Dr. Michal Zalibera Denis S. Krylov Dimitrios Karagiannis Paul‐Anton Will Frank Ziegs Sandra Schiemenz Prof. Dr. Wolfgang Lubitz Prof. Dr. Sebastian Reineke Dr. Anton Savitsky Dr. Alexey A. Popov 《Angewandte Chemie (International ed. in English)》2018,57(1):277-281
The endohedral fullerene Y3N@C80 exhibits luminescence with reasonable quantum yield and extraordinary long lifetime. By variable‐temperature steady‐state and time‐resolved luminescence spectroscopy, it is demonstrated that above 60 K the Y3N@C80 exhibits thermally activated delayed fluorescence with maximum emission at 120 K and a negligible prompt fluorescence. Below 60 K, a phosphorescence with a lifetime of 192±1 ms is observed. Spin distribution and dynamics in the triplet excited state is investigated with X‐ and W‐band EPR and ENDOR spectroscopies and DFT computations. Finally, electroluminescence of the Y3N@C80/PFO film is demonstrated opening the possibility for red‐emitting fullerene‐based organic light‐emitting diodes (OLEDs). 相似文献
123.
Large Zero‐Field Splittings of the Ground Spin State Arising from Antisymmetric Exchange Effects in Heterometallic Triangles
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Samantha A. Magee Dr. Stephen Sproules Dr. Anne‐Laure Barra Dr. Grigore A. Timco Nicholas F. Chilton Prof. David Collison Prof. Richard E. P. Winpenny Prof. Eric J. L. McInnes 《Angewandte Chemie (International ed. in English)》2014,53(21):5310-5313
[Ru2Mn(O)(O2CtBu)6(py)3] has an S=5/2 ground state with a very large zero‐field splitting (ZFS) of D=2.9 cm?1, as characterized by EPR spectroscopy at 4–330 GHz. This is far too large to be due to the MnII ion (D <0.2 cm?1), as shown from the {Fe2Mn} analogue, but can be modeled by antisymmetric exchange effects. 相似文献
124.
Dr. Kyohei Otsuka Naozumi Matsumoto Dr. Shintaro Ishida Prof. Dr. Soichiro Kyushin 《Angewandte Chemie (International ed. in English)》2015,54(27):7833-7836
The radical anion of octa‐tert‐butyloctasilacubane was generated and isolated. The EPR spectrum showed the satellites due to the tertiary 13C nuclei of the eight tert‐butyl groups. The X‐ray crystallographic analysis showed that the Si? Si bonds are shortened and the Si? C bonds are elongated compared with those of octa‐tert‐butyloctasilacubane. These results are well explained by the distribution of an unpaired electron in the singly occupied molecular orbital (SOMO). 相似文献
125.
Synthesis and EPR/UV/Vis‐NIR Spectroelectrochemical Investigation of a Persistent Phosphanyl Radical Dication
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Kai Schwedtmann Stephen Schulz Felix Hennersdorf Prof. Dr. Thomas Strassner Dr. Evgenia Dmitrieva Prof. Dr. Jan J. Weigand 《Angewandte Chemie (International ed. in English)》2015,54(38):11054-11058
The reaction of the bis(imidazoliumyl)‐substituted PI cation [(2‐ImDipp)P(4‐ImDipp)]+ ( 10 +) (2‐Im=imidazolium‐2‐yl; 4‐Im=imidazolium‐4‐yl; Dipp=2,6‐di‐isopropylphenyl) with trifluoromethanesulfonic acid (HOTf) or methyl trifluoromethylsulfonate (MeOTf) yields the corresponding protonated [(2‐ImDipp)PH(4‐ImDipp)]2+ ( 11 2+) and methylated [(2‐ImDipp)PMe(4‐ImDipp)]2+ ( 12 2+) dications, respectively. EPR/UV/Vis‐NIR spectroelectrochemical investigation of the low‐coordinated PI cation 10 + predicted a stable and “bottleable” P‐centered radical dication [(2‐ImDipp)P(4‐ImDipp)]2+. ( 13 2+.). The reaction of 10 + with the nitrosyl salt NO[OTf] yields the persistent phosphanyl radical dication 13 2+. as triflate salt in crystalline form. Quantum chemical investigation revealed an exceptional high spin density at the P atom. 相似文献
126.
B. A. Salakhutdinov D. N. Dalimov T. F. Aripov I. I. Tukfatullina R. Kh. Ziyatdinova A. Zh. Dzhuraev F. G. Kamaev L. Yu. Izotova B. T. Ibragimov I. Mavridis P. Giastas 《Chemistry of Natural Compounds》2002,38(3):249-256
Derivatives of 3-O-acetyl-18-H-glycyrrhetic acid were synthesized. Their structures and membrane activities were studied. 相似文献
127.
Antoine Aboukais Elena A. Zhilinskaya Jean-Franois Lamonier Igor N. Filimonov 《Colloids and surfaces. A, Physicochemical and engineering aspects》2005,260(1-3):199-207
Oxygen adsorption experiments were performed on evacuated and prereduced CeO2/SiO2 and CeO2/Al2O3 catalysts with and without platinum. Considerable amounts of the superoxide radical ions were stabilized on all the samples. Signal parameters suggest Ce4+–O2− positioning for all detectable superoxide species. Physisorbed oxygen broadens O2− signal beyond detection for all the alumina-based samples, while the same procedure for all the silica-based samples did not change signal shape of O2− species. Detectable O2− species are localized in the bulk of ceria and the nature of support (silica or alumina) determines the number of oxygen vacancies and the rate of electron transfer. XRD data suggest that for alumina-based samples small and/or thin islands of ceria dominate, while comparatively large ceria particles are stabilized on the surface of silica-based samples with the same ceria content. Average size of ceria crystallites is still not determining factor and cannot account for the observed differences. Higher concentrations of paramagnetic species may be stabilized on alumina-based samples and thus, sensor-like behavior towards gaseous oxygen at room temperature was detected for them—oxygen admission reversibly changes superoxide lineshape. For silica samples, only minor changes of O2− lineshapes were typical upon the change of the partial pressure of oxygen at ambient and low temperatures. Addition of platinum has little effect on parameters of the O2− signal, except an enhancement of the superoxide decay in the reducing media. Possible site for O2− stabilization inside the lattice of CeO2 was proposed and relevance of the observed effects to the redox catalysis discussed. 相似文献
128.
Zheng-Huan Lin Hong-Yan Dou Jin Li Cheng-Xue Zhao 《Research on Chemical Intermediates》2005,31(9):867-873
The H-abstractions/spin-trapping reactions with primary, secondary and tertiary alcohols of new 'magic blue' reagents, namely,
the blue F113 (CClF2CCl2F) solution containing bis{perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl} nitroxide (2) and perfluoro[1-nitroso-1-(2-fluorosulfonyl)ethoxy]ethane (3) both generated in the reaction of perfluoro[2-(2-fluorosulfonyl)ethoxy]propionyl peroxide (1) with sodium nitrite in F113 at room temperature, were studied by EPR. Based on the interpretation of the EPR spectra of
the spin adducts, nitroxides, the region-selectivity of H-abstraction has been disclosed and the possible mechanistic paths
of H-abstraction have also been discussed. EPR of H-abstraction by using 'magic blue' reagents can also be used for producing
various hydroxyalkyl radicals from common alcohols. 相似文献
129.
The electron paramagnetic resonance (EPR) spectra of gamma irradiated single crystals of alpha-benzoinoxime (ABO) have been examined between 120 and 440 K. Considering the dependence on temperature and the orientation of the spectra of single crystals in the magnetic field, we identified two different radicals formed in irradiated ABO single crystals. To theoretically determine the types of radicals, the most stable structure of ABO was obtained by molecular mechanic and B3LYP/6-31G(d,p) calculations. Four possible radicals were modeled and EPR parameters were calculated for the modeled radicals using the B3LYP method and the TZVP basis set. Calculated values of two modeled radicals were in strong agreement with experimental EPR parameters determined from the spectra. Additional simulated spectra of the modeled radicals, where calculated hyperfine coupling constants were used as starting points for simulations, were well matched with experimental spectra. 相似文献
130.
W. Russ Algar 《Analytica chimica acta》2010,673(1):1-25
A comprehensive review of the development of assays, bioprobes, and biosensors using quantum dots (QDs) as integrated components is presented. In contrast to a QD that is selectively introduced as a label, an integrated QD is one that is present in a system throughout a bioanalysis, and simultaneously has a role in transduction and as a scaffold for biorecognition. Through a diverse array of coatings and bioconjugation strategies, it is possible to use QDs as a scaffold for biorecognition events. The modulation of QD luminescence provides the opportunity for the transduction of these events via fluorescence resonance energy transfer (FRET), bioluminescence resonance energy transfer (BRET), charge transfer quenching, and electrochemiluminescence (ECL). An overview of the basic concepts and principles underlying the use of QDs with each of these transduction methods is provided, along with many examples of their application in biological sensing. The latter include: the detection of small molecules using enzyme-linked methods, or using aptamers as affinity probes; the detection of proteins via immunoassays or aptamers; nucleic acid hybridization assays; and assays for protease or nuclease activity. Strategies for multiplexed detection are highlighted among these examples. Although the majority of developments to date have been in vitro, QD-based methods for ex vivo biological sensing are emerging. Some special attention is given to the development of solid-phase assays, which offer certain advantages over their solution-phase counterparts. 相似文献